MX2012014326A - Copolymers for near-infrared radiation-sensitive coating compositions for positive-working thermal lithographic printing plates. - Google Patents
Copolymers for near-infrared radiation-sensitive coating compositions for positive-working thermal lithographic printing plates.Info
- Publication number
- MX2012014326A MX2012014326A MX2012014326A MX2012014326A MX2012014326A MX 2012014326 A MX2012014326 A MX 2012014326A MX 2012014326 A MX2012014326 A MX 2012014326A MX 2012014326 A MX2012014326 A MX 2012014326A MX 2012014326 A MX2012014326 A MX 2012014326A
- Authority
- MX
- Mexico
- Prior art keywords
- alkyl
- copolymer
- amide
- infrared radiation
- coating
- Prior art date
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
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- C07C233/00—Carboxylic acid amides
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- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/53—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/54—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
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- C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
- C08F220/346—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links and further oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
Abstract
There is provided a copolymer having the general structure below, wherein a, b, and d are molar ratios varying between about 0.01 and about 0.90 and c is a molar ratio varying between about 0,01 and about 0.90; A1 represents monomer units comprising a cyano-containing pendant group in which the cyano is not directly attached to the backbone of the copolymer; A2 represents monomer units comprising two or more hydrogen bonding sites; A3 represents monomer units that increase solubility in organic solvents; and A4 represents monomer units that increase solubility in aqueous alkaline solutions. There is also provided a near-infrared radiation-sensitive coating composition comprising this copolymer as well as a positive-working thermal lithographic printing plate comprising a near-infrared radiation-sensitive coating comprising this copolymer, a method of producing such a printing plate, and finally a method of printing using such a printing plate. Formula (I).
Description
COPOLYMERS FOR COATING COMPOSITIONS SENSITIVE TO ALMOST-INFRARED RADIATION FOR PRINTING PLATES
THERMAL LITHOGRAPHY OF POSITIVE WORK
Field of the Invention
The present invention relates to thermal lithographic printing plates and their coatings. More specifically, the invention relates to copolymers for use in near-infrared radiation sensitive coating compositions for positive working thermal lithographic printing plates.
Background of the Invention
In lithographic printing, a printing plate is mounted on the cylinder of a printing press. The printing plate has a lithographic image on its surface and a printed copy is obtained by applying ink to the image and then transferring the ink from the printing plate onto a receiving material, which is typically a sheet of paper. In general, the ink is first transferred to an unfinished intermediate part, which in turn transfers the ink to the surface of the receiving material (offset printing).
In conventional lithographic printing, called "wet", the ink as well as the aqueous ink fountain solution (also called wetting liquid) are supplied to the lithographic image consisting of oleophilic (or hydrophobic) areas, that is, they accept ink and repel water) as well as hydrophilic areas (or oleophobic, that is, they accept water and repel ink). When the surface of the printing plate is moistened with water and ink is applied, the hydrophilic regions retain water and repel ink, and the ink-receiving regions accept ink and repel water. During printing, the ink is transferred to the surface of the receiving material in which the image is to be reproduced.
Lithographic printing plates typically comprise an imageable layer (also called coating or imaging layer) applied on the hydrophilic surface of a substrate, typically aluminum. The imageable layer includes one or more radiation sensitive components, often dispersed in a suitable binder.
To produce the lithographic image on the printing plate, the printing plate is formed by radiation image directed to the target. This can be done in different ways. In the direct formation of digital images (computer to board), the printing plates can be imaged with infrared light sources or UV lasers. This laser can be controlled digitally by a computer; that is, the laser can be turned on or off so that the image-type exposure of the precursor can be affected by the digitized information stored in the computer. Therefore, the imageable layers of the printing plates that are to be imaged by means of imagers, need to be sensitive to radiation in the near-infrared (NIR) or ultraviolet (UV) regions of the spectrum . Thermal lithographic plates are plates sensitive to near-infrared radiation.
The image forming device will record the image on the printing plate by producing a localized transformation of the imageable layer. In fact, in these image-formed systems, the imageable layer typically contains a dye or pigment that absorbs the incident radiation and the energy absorbed initiates the reaction that produces the image. Exposure to radiation activates a chemical or physical process in the imageable layer so that the image areas become different from the non-image areas and the development will produce an image on the printing plate. The change in the formable layer with image can be a change of hydrophilicity / oleophilicity, solubility, hardness, etc.
After exposure, either the exposed regions or the unexposed regions of the imageable layer are removed by an appropriate developer, revealing the underlying hydrophilic surface of the substrate. The developers are typically aqueous alkaline solutions, which contain inorganic salts, such as sodium metasilicate, sodium hydroxide and potassium hydroxide and surfactants.
Alternatively, the "print-able" lithographic printing plate can be mounted directly on a press after image forming, and is revealed through contact with ink and / or ink fountain solution during the initial operation of the press . In other words, either the exposed regions or the unexposed regions of the imageable layer are removed by the ink and / or the ink fountain solution, not by a developer. More specifically, a so-called press development system is one in which an exposed printing plate is fixed on the plate cylinder of a printing press, and an ink fountain and ink solution are fed thereto as long as it is rotate the cylinder to remove the non-image areas. This technique allows a print plate with an image, but not revealed (also called a printing plate precursor) to be mounted as it is in a press and is made in a printing press on an ordinary printing line.
If the exposed regions are removed, the precursor is positive work. On the contrary, if the unexposed regions are removed, the precursor is negative work. In each case, the regions of the imageable layer (i.e., the image areas) that remain are ink receptors, and the hydrophilic surface regions revealed by the development process accept water and aqueous solutions, typically a solution of inkwell and do not accept ink.
It is known in the art to use copolymers comprising a cyano (-CN) group directly attached to the polymer structure to produce offset, lithographic, thermal, positive-working, single-plate and multi-layer printing plates. These copolymers with cyano (-CN) group directly attached to the polymer structure typically provide good film-forming properties, mechanical strength and chemical resistance in the press.
Acrylonitrile and methacrylonitrile are liquids with a low boiling point (< 100 ° C). Recently they have been classified as hazardous and very toxic materials. In this way they require special handling and permission for transportation. The acrylonitrile and methacrylonitrile residues can not be released from a product with an excess of 1 ppm (concentration in air) as a weighted average in a time of eight (8) hours, under the expected conditions of processing, use, and handling. This requirement is very difficult to achieve when copolymers containing acrylonitrile and methacrylonitrile are used for the production of offset, lithographic printing plates.
Brief Description of the Invention
In accordance with the present invention, it is provided:
1. A copolymer having the general structure
where
a, b, and d are molar ratios ranging from about 0.01 to about 0.90 and c is a molar ratio ranging from 0 to about 0.90,
Al represents monomeric units comprising a pendant group containing cyano in which the cyano is not directly attached to the structure of the copolymer;
A2 represents monomer units comprising two or more hydrogen bonding sites;
A3 represents monomer units that increase the solubility in organic solvents; Y
A4 represents monomer units that increase the solubility in aqueous alkaline solutions.
2. The copolymer of point 1, where Al is of the formula:
where:
R is hydrogen, methyl or ethyl,
Ri is absent or represents one to four alkyl substituents; alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups, alkyl substituents which are optionally substituted with one or more cyano groups,
Ui is an amide or ester linker,
Vi is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, alkyl which is optionally substituted with one or more cyano group, and
wherein R is hydrogen, methyl or ethyl and n varies between 1 and 10.
4. The copolymer of any of items 1 to 3, wherein A2 comprises a pendant group comprising a 5,5-dialkylhydantoin group such as a 5,5-dimethylhydantoin group, an aminosulfonamide group or a hydroxy group.
5. The copolymer of any of items 1 to 3, wherein A2 is of the formula:
where:
R is hydrogen, methyl or ethyl,
Ri is absent or represents from one to four alkyl substituents, alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups,
U2 is absent or represents an amide or ester linker,
V2 is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, and
wherein R2 each time it occurs is independently hydrogen or alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups.
6. The copolymer of point 5, where Y is
7. The copolymer of point 5, where A2 is:
?? 8. The copolymer of any of items 1 to 7, wherein c varies from about 0.01 to about 0.90.
9. The copolymer of item 8, wherein A3 comprises an alkyl or aryl pendant group, the aryl which is optionally substituted with alkyl.
10. The copolymer of point 8, wherein A3 is of the formula:
where
R is hydrogen, methyl or ethyl,
U3 is absent and is an amide or ester linker, and
Z is alkyl or aryl, alkyl that is optionally substituted with one or more hydroxy, alkyloxy or halide groups and the aryl which is optionally substituted with one or more alkyls that are optionally substituted with one or more hydroxy, alkyloxy or halide.
11. The copolymer of point 9, where A3 is:
wherein R is hydrogen, methyl or ethyl.
12. The copolymer of any of the points 1 to
10, wherein A4 comprises a pendant group comprising a carboxylic acid group or a phosphoric acid group.
13. The copolymer of any of the points 1 to
11, where A4 is of the formula:
wherein R is hydrogen, methyl or ethyl,
Ri is absent or represents one to four alkyl substituents; alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups,
U4 is absent or represents an amide or ester linker,
V4 is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, and
14. The copolymer of any of the points 1 to
12, wherein A4 is a monomer unit obtained by polymerizing monomers of acrylic acid, methacrylic acid, 4-carboxyphenylmethacrylamide, 4-carboxyphenylacrylamide, vinylbenzoic acid, vinylphosphoric acid, methacrylyl-alkyl-phosphoric acid, or acrylyl-alkyl acid -phosphoric.
15. A radiation-sensitive, near-infrared coating composition comprising:
- a copolymer as defined in any of items 1 to 13;
- a binder resin;
- an almost infrared radiation absorption compound; Y
- optional additives.
16. A positive working thermal lithographic printing plate comprising a coating sensitive to near-infrared radiation throws the coating which is a coating prepared from the coating composition of point 14.
17. A lithographic, thermal, positive working printing plate comprising a coating that is sensitive to near infrared radiation, the coating comprising:
- a copolymer as defined in any of items 1 to 13;
- a binder resin;
a compound that absorbs near-infrared radiation; Y
- optional additives.
18. A method for producing a lithographic, thermal, positive working printing plate, the method comprising the steps of:
a) provide a substrate, and
b) coating the coating composition of point 14 on the substrate.
19. A printing method, the method comprising the steps of:
a) provide a lithographic printing plate, thermal, positive work according to point 15 or 16,
b) image forming the printing plate with near-infrared radiation,
c) reveal the printing plate, and
d) using the printing plate in a printing press for printing.
e) using the printing plate in a printing press for printing.
20. A monomer corresponding to a monomeric unit Al as defined in any of points 1 to 3.
21. A monomer corresponding to a monomeric unit A2 as defined in any of points 1 and 4 to 7.
22. A monomer corresponding to a monomer unit A3 as defined in any of points 1 and 9 to 11.
23. A monomer corresponding to an A4 monomer unit as defined in any of points 1, 12, and 13.
Detailed description of the invention
Copolymers for Lithographic, Thermal, Positive Work Printing Plates
Turning now to the invention in more detail, there is provided a copolymer comprising Al monomer units, which are monomer units comprising a pendant group containing cyano in which the cyano is not directly bonded to the copolymer structure and at least one other type of monomer units.
As used herein, a "copolymer" is a polymer produced from at least two different types of monomer units. These monomer units are relatively small molecules linked with relatively large numbers of other monomer units to form a chain, i.e., a polymer or copolymer. As used herein, the "structure" of a polymer or copolymer means the series of covalently bonded atoms of the monomer units which together create the continuous chain of the polymer or copolymer. A "hanging group" is a group of atoms attached to but not part of, the structure of the copolymer.
As such, then, a "pendant group containing cyano" is a pendant group comprising a cyano group (-C = N). Thus, in the above, the cyano group, which is comprised in a pendant group, is not directly linked to the structure of the copolymer; rather it is linked to the hanging group, which in turn is linked to the structure as in the more specific modalities shown below. More specifically, the monomeric unit that has a pendant group containing cyano group does not
it can be where R is any hanging group. Rather this monomeric unit can be of the
formula: where R and Q are any hanging group.
In the present, a "monomer" is a compound that becomes a monomer unit in the polymerization. By
eg the monomer produced by the unit
monomeric in a polymer or copolymer,
The copolymer is for use in near-infrared radiation sensitive coating compositions for lithographic, thermal, positive working printing plates. In embodiments, the copolymer can be a high molecular weight copolymer, ie, a copolymer with a molecular weight of 10,000 g / mol and more.
In embodiments, the copolymer has the general structure:
wherein a, b, and d are molar ratios ranging from about 0.01 to about 0.90 and c is a molar ratio ranging from about 0 to about 0.90.
Al represents monomeric units comprising a pendant group containing cyano in which the cyano is not directly attached to the structure of the copolymer;
A2 represents monomer units comprising two or more hydrogen bonding sites;
A3 represents monomer units that increase the solubility in organic solvents; Y
A4 represents monomer units that increase the solubility in aqueous alkaline solutions.
It is to be understood from the above general structure that the copolymer can simultaneously comprise two or more different Al monomer units, two or more different A2 monomer units, two or more different A3 monomer units and / or two or more different A4 monomer units.
In the above, c can be 0, which means that A3 is optional. In this way, in modalities, A3 is absent from the previous chemical structure. In other embodiments, c ranges from about 0.01 to about 0.90. In modalities, a, b, c, and / or od are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8 or more and / or are 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 or less.
In modalities, Al is of the formula:
where:
R is hydrogen, methyl or ethyl,
Ri is absent or represents one to four alkyl or alkoxy substituents; alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups, alkyl substituents which are optionally substituted with one or more cyano groups,
Ui is an amide or ester linker,
Vi is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, alkyl which is optionally substituted with one or more cyano groups, and
In the present, when it is said that an alkyl comprises (or optionally comprises) a functional group, it means that the functional group may be either at the alkyl end or between any two carbon atoms of the alkyl. For more certainty, when more than one functional group is comprised in an alkyl, the functional groups do not need to be separated by carbon atoms of the alkyl; that is, they can be directly linked together. It is understood that when this functional group (which has two bonds available as shown below) is located at one end of the alkyl, one of its two available bonds will be attached to the terminal carbon atom of the alkyl and the other will be attached to an atom. of hydrogen.
In the present, when an alkyl is said to be substituted (or optionally substituted) with a group, this expression has its usual meaning in the art, that is, one of the hydrogen atoms of the alkyl is replaced by the group.
For more certainty, in the present an ether functional group is -0-; an ester functional group (or linker) is - (C = 0) -O- or -0- (C = 0) -; an amine functional group is -NR3-, an amide functional group (or linker) is - (C = 0) -NR3- or -NR3- (C = 0) -; a functional group urea is -NR3- (C = 0) -NR3-; a group
Functional piperazinyl is a sulfonamide functional group is -S02-NR3- or -NR3-S02-; and a carbamate functional group is -NR3- (C = 0) -O- or -O- (C = 0) -NR3-. In these functional groups, R3 is hydrogen or alkyl, the alkyl which is optionally substituted with one or more of hydroxy, alkyloxy or halide.
In modalities, Al is
wherein R is hydrogen, methyl or ethyl and n varies between 1 and 10.
In a related aspect, the present invention also relates to monomers. More specifically, the present invention relates to monomers corresponding to any and all monomeric units Al described above, individually or as a group, as well as to any and all subsets thereof.
For reasons of concision, the formulas of these monomers are not repeated in the present. The skilled person will easily infer these formulas from the formulas of the monomeric units Al given above. Actually, as used herein, a "monomer" is a compound that becomes a monomeric unit in the
polymerization. For example, the monomer that
produces the monomer unit in a polymer or copolymer. The skilled person will readily appreciate that the monomer corresponding to any given monomeric unit will be identical to that monomeric unit except that the two bonds linking the monomeric unit to the other two monomer units (left and right in the above formula) are they replace by a double bond.
As noted above, A2 is a monomer unit comprising two or more hydrogen bonding sites. In embodiments, A2 comprises three, four or five hydrogen bonding sites. A2 comprises functional groups capable of forming hydrogen bonds. These functional groups are well known to the person skilled in the art include groups containing a hydrogen atom in a polar covalent bond and groups containing an electronegative atom with a pair of free electrons. Non-limiting examples of these groups include hydroxy, carboxy, esters, amines, amides and groups obtained by combining these.
In specific modalities, A2 is of the formula
where:
R is hydrogen, methyl or ethyl,
Ri is absent or represents from one to four alkyl substituents, alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups,
U2 is absent or represents an amide or ester linker,
V2 is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, and
wherein R2 at each occurrence is independently hydrogen or optionally alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups.
In embodiments, A2 comprises a pendant group comprising a 5, 5-dialkylhydantoin such as the group 5,5-
say, a group like-NH-C6H -S02- H2), or a group
??
, wherein R is hydrogen, methyl or ethyl.
In a related aspect, the present invention also relates to monomers. More specifically, the present invention relates to monomers corresponding to any and all monomer units A2 described above, individually or together as a group, as well as any and all subsets thereof.
For reasons of concision, the formulas of these monomers are not repeated in the present. The skilled person will easily infer these formulas from the formulas of the monomer units? 2 given above. Actually, as used herein, a "monomer" is a compound that becomes a monomer unit in the polymerization. For example, the monomer that
produces the monomer unit in a polymer or copolymer. The skilled person will readily appreciate that the monomer corresponding to any given monomeric unit will be identical to that monomeric unit except that the two bonds linking the monomeric unit to the other two monomer units (left and right in the previous formula) they are replaced by a double bond.
As noted above, A3 is a monomer unit that is increased in organic solvents. Organic solvents include those typically used in the manufacture of thermal lithographic printing plates; for example: alcohol, ketone, N, N, -dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dioxolane and other common polar solvents.
In embodiments, A3 comprises an alkyl or aryl pendant group. The alkyl and aryl groups increase the solubility in organic solvents. The solubility of the copolymer in this way can be modulated by varying the molar ratio c.
modalities, A3 is of the formula
where
R is hydrogen, methyl or ethyl,
U3 is absent or represents an amide or ester linker, and
Z is alkyl or aryl, alkyl that is optionally substituted with one or more of hydroxy, alkyloxy or halide and the aryl which is optionally substituted with one or more alkyls that are optionally substituted with one or more of hydroxy, alkyloxy or halide.
.
In a related aspect, the present invention also relates to monomers. More specifically, the present invention relates to monomers corresponding to any and all A3 monomer units described above, individually or together as a group, as well as any and all subsets thereof.
For reasons of concision, the formulas of these monomers are not repeated in the present. The skilled person will easily infer those formulas from the formulas of the A3 monomer units given above. Actually, as used herein, a "monomer" is a compound that becomes a monomeric unit in the
polymerization. Po the monomer that
produces the unit in a polymer or copolymer. The skilled person will readily appreciate that the monomer corresponding to any given monomer unit will be identical to this monomer unit except that the two bonds linking the monomer unit to the other two monomer units (left and right in the above formula) are they replace by a double bond.
As noted above, A4 increases the solubility in aqueous alkaline solutions. In this way,
A4 typically comprises a pendant group comprising an acid functional group, such as a carboxylic acid (-COOH) or a phosphoric acid (-PO (OH) 2). These acid functional groups increase the solubility in aqueous alkaline solutions. The solubility of the copolymer in this way can be modulated by varying the molar ratio d.
In specific modalities, A4 is of the formula:
wherein R is hydrogen, methyl or ethyl,
R x is absent or represents one to four alkyl substituents; alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups,
U is absent or represents an amide or ester linker,
V4 is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, and
In embodiments, A4 is a monomeric unit obtained by polymerizing monomers of acrylic acid, methacrylic acid, 4-carboxyphenylmethacrylamide, 4-carboxyphenylacrylamide, vinylbenzoic acid, vinyl phosphoric acid, methacrylyl-alkyl-phosphoric acid, or acrylyl-alkyl acid. phosphoric
In a related aspect, the present invention also relates to monomers. More specifically, the present invention relates to monomers corresponding to any and all A4 monomer units described above, individually or together as a group, as well as any and all subsets thereof.
For reasons of concision, the formulas of these monomers are not repeated in the present. The skilled person will easily infer these formulas from the formulas of the A4 monomer units given above. Actually, as used herein, a "monomer" is a compound that becomes a monomer unit in the polymerization.
For example, it is the monomer that produces the unit
monomeric in a polymer or copolymer. The skilled person will readily appreciate that the monomer corresponding to any given monomeric unit will be identical to that monomeric unit except that the two bonds linking the monomeric unit to the other two monomer units (left and right in the above formula) are they replace by a double bond.
Methods for Making Copolymers
The copolymers of the invention typically have reduced toxicity and are easy and inexpensive to produce. They can be obtained by copolymerizing the corresponding monomers in organic solvents using free radical initiators. Examples of these initiators include 2,2'-azobis (2-methylbutyronitrile), benzoyl peroxide, and ammonium persulfate. The resultant copolymers are isolated by precipitation in water or mixtures of water and alcohol, filtered and dried to constant weight.
Coating Compositions Sensitive to Near-Infrared Radiation for Lithographic, Thermal, Positive Work Printing Plates
In another aspect, the present invention relates to the use of the copolymers described above in near-infrared radiation sensitive coating compositions for lithographic, thermal, positive working, single or multiple layer printing plates. These plates can be formed directly with images with near-infrared laser imaging devices in digital offset and computer-to-plate printing technologies.
Thus, the present invention relates to a near-infrared radiation sensitive coating composition for a lithographic, thermal, positive working printing plate, the composition comprising:
- a copolymer as defined above, preferably in an amount between about 15 and about 85% by weight;
- a binder resin, preferably in an amount between about 15 and about 85% by weight;
an absorber of near-infrared radiation, preferably in an amount between about 1.0 and about 15% by weight; Y
optional additives, preferably an amount between 0.50 and approximately 2.0% by weight.
It is to be understood from the foregoing that the coating composition may comprise a mixture of copolymers, a mixture of binder resins, a mixture of near-infrared radiation absorbing compounds, and / or a mixture of optional additives, such as visible dyes. , film-forming additives and stabilizers.
These coating compositions can be used to prepare a coating for a lithographic, thermal, positive working printing plate. The coating composition is sensitive to radiation since, on exposure to radiation, there will be a chemical or physical process in the coating (produced using the coating composition) so that 1) the image areas will be different from the non-image areas after exposure to radiation and 2) the development will produce an image on the printing plate.
Bonding resins
According to the present invention, the coating composition comprises binder resins, preferably in an amount between about 15-20% and about 80-85% by weight. The binder resins suitable for use in lithographic, positive working thermal printing plates are well known to the person skilled in the art.
Examples of binder resins include polymers and copolymers comprising hydroxy groups that can form a hydrogen bond network with the copolymers of the invention. These binder resins are, for example, phenolic resins, acetal copolymers and cellulose polymers. In embodiments, the binder resin is ThermolakMR 7525 (a phenolic resin, available from American Dye Source, Inc., Baie d'Urfe, Quebec, Canada), ThermolakMR 0802 (an acetal copolymer, available from American Dye Source, Inc., Baie d'Urfe, Quebec, Canada) and cellulose acetate acid phthalate (available from Kodak, Kingsport, Tennessee, USA).
Almost-Infrared Radiation Absorber Compound
According to the present invention, the coating composition further comprises an almost-infrared radiation absorbing compound, preferably in an amount between about 1.0 and about 15% by weight. Near-infrared radiation absorbing compounds, suitable for use in lithographic, thermal, positive working printing plates, are well known to the person skilled in the art. These near-infrared radiation absorbing compounds have one or more absorption bands between about 780 and about 1,100 nm. These materials convert the near-infrared radiation into incoming heat.
Suitable near-infrared radiation absorbing compounds are, for example, molecular cyanine dyes and merocyanine, as described in U.S. Patent Nos. 5,397,690 and 6,326,122, which are incorporated herein by reference. Other examples of molecular dyes absorbing near-infrared radiation include the following, which are available from American Dye Source, Inc., Baie d'Urfe, Quebec, Canada:
ADS821AT.
Other suitable near-infrared radiation absorbing compounds are the polymers described in US 6,124,425; 6,177,182; and 7,473,515, which is incorporated herein by reference. Still other suitable near-infrared radiation absorbing polymers are available from American Dye Source, Inc., Baie d'ünle, Quebec, Canada, and have the following structures:
Thermolak® 8010
where a, b, c, d, and e are the molar ratios, which are 0.10, 0.30, 0.50, 0.08 and 0.02, respectively; Y
CIO
Thermolak® 1010
where a, b, and c are the molar ratios, which are 0.73, 0.25, and 0.02 respectively.
The amount of these near-infrared radiation absorbing polymers in the coating composition is preferably between about 7 and about 15 weight percent.
Other near-infrared radiation absorbing materials that may be used in the coating composition of the present invention may be the quasi-infrared radiation absorber, galotannin compounds described in Provisional Patent Application 61 / 255,918, which is incorporated herein by reference. as reference. These compounds are available from American Dye Source, Inc., Baie d'ürfe, Quebec, Canada. An example of this galotánnico compound is:
Thermolak® 9031
The amount of these quasi-infrared radiation absorber galotanic compounds is preferably between about 2 and about 5 weight percent.
Optional additives
Optional additives that can be used in the coating composition described above include, for example, visible dyes, film-forming agents and shelf-life stabilizers. These additives and their use are well known to those skilled in the art.
In embodiments, visible dyes having absorption bands between 450 and 780 nm are used, preferably in an amount between about 1 and about 5 weight percent. Examples of these visible dyes include cationic dyes, such as basic blue 3, basic blue 7, basic blue 11, basic blue 17, basic blue 26, basic blue 66, basic red 9, basic red 29, basic violet 2, basic violet 3, basic violet 4, basic violet 6, basic violet 14, basic green 4 and basic green 5.
The coating composition may further comprise film forming agents to provide more uniformly coated films and to provide a more slippery upper surface to reduce scratching during handling and packaging. Examples of film-forming agents include siloxane copolymers having pendant polyether, polyester and alkyl groups, such as that commercially available from BYK USA (Wallingford, Connecticut, USA) under the trade names BYK 306, BYK 307, BYK 310, BYK 333, and BYK 337. Another suitable film-forming agent is a siloxane copolymer comprising polyether and alkyl pendant groups available from American Dye Source, Inc. under the trade name ThermolakMR P1000S. The amount of film-forming agents in the coating compositions is preferably between about 1 and about 6 weight percent.
The coating composition may additionally comprise shelf life stabilizers such as that described in U.S. Patent No. 6,884,568, including 3-mercapto-1,2,4-triazole; 3-mercapto-methyl-4H-1, 2,4-triazole; 3-mercapto-5- (4-pyridyl) -1H-1,2,4-triazole; 2-mercaptobenzimidazole; 2-mercaptobenzoxazole;
2-mercaptobenzothiazole; 6-ethoxy-2-mercaptobenzothiazole; 2-mercapto-5-methyl-l, 3, 4-thiadiazole; 2-mercapto-5-phenyl-1,3,4-oxadiazole; 2-mercapto-5- (4-pyridyl) -1, 3, 4-oxadiazole; 5-mercapto-3-methylthio-1,2,4-thiadiazole; 2-mercapto-5-methylthio-1,3,4-thiadiazole; 2-mercaptoimidazole; 2-mercapto-l-methylimidazole; 5-mercapto-l-methyl-lH-tetrazole; and 5-mercapto-1-phenyl-lH-tetrazole. The amount of thermal stabilizers in the coating compositions is preferably between about 1 and about 4 weight percent.
The coating composition may also comprise one or more suitable solvents. The solvent allows the formation of a coating on a substrate. Any solvent known to the person skilled in the art may be used as is appropriate for this purpose. Non-limiting examples of this solvent include n-propanol, isopropanol, 2-methoxy propanol, ethyl glycol, water or a mixture thereof.
Plates Lithographic, Thermal, Positive Work and Methods to Produce and Use
In another aspect, the present invention relates to a positive working thermal lithographic printing plate comprising an almost-infrared radiation sensitive coating, the coating being a coating prepared from the coating composition described above.
In another related aspect, the present invention relates to a lithographic, thermal, positive working printing plate comprising a coating sensitive to near-infrared radiation, the coating comprising:
- a copolymer as defined above;
a binder resin as defined above;
an almost-infrared radiation absorbing compound as defined above; Y
Optional additives as defined above.
On the printing plate, the coating sensitive to near-infrared radiation is deposited on a substrate. In modalities, the substrate is anodized aluminum, plastic films or paper. Aluminum substrates can be treated with grain and brushed or treated with grain and electricity, then anodized with acid solutions. The coating that is sensitive to near-infrared radiation may have a coating weight of between about 1.0 and about 3.0 g / m2.
In embodiments, there may be one or more layers between the substrate and the coating sensitive to near-infrared radiation and / or on the upper part of the coating sensitive to near-infrared radiation as known to the person skilled in the art. For example, a polymeric adhesion promoter layer and / or heat insulator may be present between the substrate and the near-infrared radiation sensitive coating. This layer can be obtained from aqueous solutions containing poly (acrylic acid), poly (acrylic acid-co-vinylphosphoric acid) or polyvinylphosphoric acid, which are then dried using hot air at about 110 ° C. The coating weight of the adhesion promoter and / or heat insulator layer may be between about 0.1 and about 1.0 g / m2. Overcoating layers may also be provided in the upper part of the coating that is sensitive to near-infrared radiation. These layers typically protect coatings sensitive to near-infrared radiation from harmful ambient radiation, moisture, graying, stickiness, etc.
In another related aspect, the present invention relates to a method for producing a lithographic, thermal, positive working printing plate, the method comprising the steps of: a) providing a substrate and b) coating a coating composition as defined previously on the substrate. In embodiments, the method further comprises the step of coating the substrate with a polymeric adhesion promoter and / or heat insulator layer, before step b).
In another related aspect, the present invention relates to a printing method, the method comprising the steps of: a) providing a lithographic printing plate, positive working thermal as defined above, b) image forming the printing plate with near-infrared radiation, c) revealing the printing plate and ) use the printing plate in a printing press for printing. The printing plates can be imaged directly with laser imaging devices in digital offset and computer-to-plate printing technologies. In embodiments, the plate with image is revealed from the press with water or with a developer.
In use, the copolymer and the binder in the coating will produce a cohesive network by forming hydrogen bonds. On exposure to near-infrared radiation, the near-infrared radiation observing compound will absorb incoming near-infrared radiation and produce heat. The heat will break the network of hydrogen bonds in the areas with image. This will make the imaged areas more soluble in water or in the developer (developed outside of the press) or ink solution and inks (developed in the press) than the unexposed areas, which will remain less soluble. This will allow the development (in press or out of press) of the printing plates.
Some of the compounds described herein may exist as isomers of different types (optical, geometric and / or positional isomers, by way of example). The present invention encompasses all these isomers.
Unless otherwise indicated, as used herein, "alkyl" means a linear or branched alkyl group having from 1 to 24 carbon atoms and "aryl" means an aryl group having from 1 to 3 cycles and optionally comprising one or two heteroatoms, such as N, 0 and S. Similarly, "alkyloxy" means a linear or branched (R-0-) alkyloxy group comprising from 1 to 24 carbon atoms.
As used herein, "halide" means F-, Cl-, Br- or herein, unless otherwise indicated, the weight percent values are based on the total dry weight of the coating composition.
As used herein, "near-infrared radiation" means electromagnetic radiation, such as that emitted by a laser, with a wavelength between about 700 and about 1100 nm. Non-limiting examples of this near-infrared radiation is the light emitted by diode lasers, which are equipped with available plate-setters from Creo-Kodak, Dinippon Screen, Heidelberg and Presstek International.
As used herein, "approximately" means about 5% of the numerical value so qualified.
Other objects, advantages and characteristics of the present invention will become more evident when reading the following non-restrictive description of specific modalities thereof, given only by way of example with reference to the appended figures.
Description of Illustrative Modalities
The present invention is illustrated in further detail by the following non-limiting examples. These examples use the compounds listed in the following glossary.
Glossary
Synthesis of Copolymers
The syntheses of the copolymers were carried out in a 4-neck glass reactor equipped with a water condenser, a mechanical stirrer, a dropping funnel and a nitrogen gas inlet. The molecule structures of the copolymers obtained were determined by FTIR and proton R N spectroscopy. The average molecular weight of the copolymers obtained was determined by size exclusion chromatography (SEC), using a solution of N, -dimethylformamide and calibrated with polystyrene standards. The acid number was determined by titration with a solution of potassium hydroxide in ethanol.
Example 1
Copolymer PCN-01A that has a general structure as shown below:
where a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized by adding 0.30 grams of V59 in 120 ml of a solution in DMF (in which 0.20 moles of MCN-01, 0.37 moles of HDB-01, 0.35 moles of ethyl methacrylate and 0.08 moles of methacrylic acid were dissolved) at 75 ° C under constant stirring and nitrogen atmosphere. After 10 hours of polymerization, 0.20 grams of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. Air was introduced and the reaction mixture was stirred at 105 ° C for an additional 2 hours to determine the polymerization. The copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the average molecular weight and the Acidity Index are 43.400 g / mol and 26.2 mg KOH / g, respectively.
Example 2
Copolymer PCN-02A that has a general structure as shown below:
where a = 0.20, b = 0.37, c = 0.35 and d = 0.08 was synthesized by adding 0.30 grams of V59 in 120 ml of a solution in DF (in which 0.20 moles of MCN-01, 0.37 moles of HDB were dissolved) 02, 0.35 moles of ethyl methacrylate and 0.08 moles of methacrylic acid) at 75 ° C under constant agitation and nitrogen atmosphere. After 10 hours of polymerization, 0.20 grams of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. Air was introduced and the reaction mixture was stirred at 105 ° C for an additional 2 hours to determine the polymerization. The copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the average molecular weight and the acid number were 74,000 g / mol and 26.4 mg KOH / g, respectively.
Example 3
Copolymer PCN-03A that has a general structure as shown below:
wherein a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized in a manner similar to Example 1 with the exception that 0.37 moles of HDB-03 replaced the HDB-01. After polymerization, the copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the molecular weight and the acid number are 85,000 mol / g and 24.4 g / mol, respectively.
Example 4
Copolymer PCN-04A that has a general structure as shown below:
wherein a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized in a manner similar to Example 1 with the exception that 0.37 moles of HDB-04 replaced the HDB-01. After polymerization, the copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the molecular weight and the acid number are 97,000 mol / g and 24.0 g / mol, respectively.
Example 5
Copolymer PCN-05A that has a general structure as shown below:
wherein a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized in a manner similar to Example 1 with the exception that 0.37 moles of HDB-05 replaced the HDB-01. After polymerization, the copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the molecular weight and the acid number are 89,000 mol / g and 23.7 g / mol, respectively.
Example 6
Copolymer PCN-06A that has a general structure as shown below:
where a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized by adding 0.30 grams of V59 in 120 ml of a solution in DMF (in which 0.20 moles of CN-02, 0.37 moles of HDB were dissolved) 02, 0.35 moles of ethyl methacrylate and 0.08 moles of methacrylic acid) at 75 ° C under constant agitation and nitrogen atmosphere. After 10 hours of polymerization, 0.20 grams of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. Air was introduced and the reaction mixture was stirred at 105 ° C for an additional 2 hours to complete the polymerization. The copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder of the copolymer was obtained after drying under vacuum at 40 ° C. The average molecular weight and the acid number were determined to be 67,000 g / mol and 23.6 mg KOH / g, respectively.
Example 7
Copolymer PCN-07A that has a general structure as shown below:
where a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized in a similar manner to Example 6 with the exception that MCN-02 was replaced by 0.20 moles of MCN-04. After polymerization, the copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the molecular weight and the acid number are 77,000 mol / g and 24.2 g / mol, respectively.
Example 8
Copolymer PCN-OSA that has a general structure as shown below:
where a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized by adding 0.30 grams of V59 in 120 ml of a solution in DMF (in which 0.20 moles of MCN-02, 0.37 moles of HDB were added) -04, 0.35 moles of ethyl methacrylate and 0.08 moles of methacrylic acid) at 75 ° C under constant stirring and nitrogen atmosphere. After 10 hours of polymerization, 0.20 grams of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. Air was introduced and the reaction mixture was stirred at 105 ° C for an additional 2 hours to complete the polymerization. The copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the average molecular weight and the Acidity Index are 105,000 g / mol and 23.9 mg KOH / g, respectively.
Example 9
PCN-09A copolymer that has a general structure as shown below:
wherein a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized in a manner similar to Example 8 with the exception that 0.37 moles of HDB-06 were used to replace the HDB-04. After the synthesis, the copolymer was synthesized in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. It was determined that the average molecular weight and the acid number are approximately 92,000 g / mol and 24.0 mg KOH / g, respectively.
Example 10
PCN-10A copolymer that has a general structure as shown below:
wherein a = 0.20, b = 0.37, c = 0.35 and d = 0.08 were synthesized in a manner similar to Example 9 with the exception that 0.20 moles of CN-03 were used to replace the MCN-02. After the synthesis, the copolymer was precipitated in 2 L of demineralized water, filtered and washed copiously with demineralized water. A white powder was obtained after drying under vacuum at 40 ° C. The average molecular weight and the acid number were determined to be approximately 82,000 g / mol
and 24.0 mg KOH / g, respectively.
Positive Working Thermal Lithographic Offset Printing Plates
Examples 11 to 21
Coating solutions were coated with the following compositions (Table I) using a rotary coating apparatus on aluminum substrate, which was electrotreated with grain using a mixed acid solution, i.e., hydrochloric acid and acetic acid, anodized in an aqueous solution of sulfuric acid, then treated with aqueous NaF / NaH2P04 solution at 80 ° C. The coated films were dried at 100 ° C with hot air. The weight obtained from the coating was approximately 1.7 g / m2.
After they are stored at 35 ° C for 1 week, the plates are imaged using a PlateRite 8600S plate setter (available from Screen, Japan) at a drum speed of 900 RPM using different laser power. The plates with image were revealed using the GSP90 developer with the TungSung 88 processor at 23 ° C.
The optical density of the printing plates was measured using a Shamrock Densitometer densitometer (Model: Color Print 415, available from Muller B.V., P.O. Box 44, 7913 ZG Hollandscheveld, The Netherlands). The percentage of spots on the revealed plates was measured using a Techkon SpectroPlate measuring device (Model: Expert, available from Techkon USA LLC, Danvers, MA 01923, USA).
The printing tests were performed on the plates developed using a Heidelberg SpeedMaster 74 press (Heidelberg, Germany) using 24/7 black sheetfed ink (available from Toyo Ink, USA).
The chemical resistance tests were performed by immersing the developed plates in alcohol-water solutions and in an ink fountain concentrate solution for 60 minutes at 25 ° C. The optical density of the plates before and after immersion in the alcohol solutions and in the inkwell solution were recorded for calculation of the chemical resistance, which was denoted as CR.
Definitions
The Correct Exposure (CE, mJ / cm2) is the requirement for energy density of image formation that has to be 50% of points on the revealed plate that coincides with 50% of points on the target.
The Cleaning Point (CP, mJ / cm2) is the energy density required to have the optical density at 0% of points equal to the optical density at 100% of points, time 0.05.
The Coating Development Loss (CDL,%) is calculated using the following equation:
COL = [ODadl -ODsub] / [ODbdi- ODsub] x 100 where:
ODgdi is the optical density at 100% points after development;
ODsub is the optical density of the uncoated aluminum substrate; Y
ODbdi is the optical density of 100% solids before development.
Small values of CE, CP and CDL indicate better performance of the printing plate.
The chemical resistance (CR,%) was calculated using the optical density change and the following equation:
CR = [ODad2- 0Dsub] / [0Dbd2- 0D3ub] x 100
where :
ODad2 is the optical density at 100% of points after development and after immersion in an alcoholic solution for 30 minutes at 25 ° C;
ODsub is the optical density of the uncoated aluminum substrate; Y
ODbd2 is the optical density of 100% solids after the development and before the immersion of an alcohol solution.
Table 1
It can be seen from this table that the printing plates comprising the polymers of the invention showed several advantages compared to the printing plate without any copolymer (Example 21). They required less energy for laser imaging, showed less loss of coating development. They also exhibited better chemical resistance against alcohol-substituted inkwell solution, such as Stabilat D2010 and water solution containing 60% Dowanol PM and propylene glycol. In contrast, it was observed that the coating of the printing plate of Example 21 was totally dissolved 8 hours after immersion in. an aqueous solution containing 50% Dowanol PM.
In addition, the printing plates comprising the copolymers of the invention produced more than 180,000 high quality copies on paper. In contrast, the plate of Example 21 produced about 110,000 high quality copies.
Finally, it was observed that the printing plates were stable during storage for at least 12 months under normal environmental conditions.
The above tests show that copolymers for positive working printing plates typically provide faster speed of laser imaging, high resolution images, wide processing latitude, stable shelf life, good chemical resistance and long print run at press
Although the invention has been described above in the manner of specific embodiments thereof, it can be modified without departing from the spirit and nature of the present invention as defined in the appended claims.
References
The present disclosure relates to several documents, the content of which is hereby incorporated by reference in its entirety:
United States Patent: 6,884,568; 5,397,690;
6,124,425; 6,132,929; 6,177,182; 6,326,122; 6,355,396;
6,410,203; 7,060,415; 7,060,416; 7,258,961; 7,371,504; and 7,473, 515.
United States Provisional Patent Application:
61/255, 918
Claims (1)
- REVINDIATIONS 1. A copolymer having the general structure: characterized because a, b, and d are molar ratios ranging from about 0.01 to about 0.90 and c is a molar ratio ranging from 0 to about 0.90, Al represents monomer units comprising a pendant group containing cyano in which the cyano is not directly bound to the structure of the copolymer; A2 represents monomer units comprising two or more hydrogen bonding sites; A3 represents monomer units that increase the solubility in organic solvents; Y A4 represents monomer units that increase the solubility in aqueous alkaline solutions. 2. The copolymer according to claim 1, characterized in that Al is of the formula: R _, where : R is hydrogen, methyl or ethyl, Ri is absent or represents one to four alkyl substituents; alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups, alkyl substituents which are optionally substituted with one or more cyano groups, Ui is an amide or ester linker, Vi is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, alkyl which is optionally substituted with one or more cyano group, and 3. The copolymer according to the indication 1 or 2, characterized in that Al is ?? wherein R is hydrogen, methyl or ethyl and n varies between 1 and 10. 4. The copolymer according to any of claims 1 to 3, characterized in that A2 comprises a pendant group comprising a 5,5-dialkylhydantoin group such as a 5,5-dimethylhydantoin group, an aminosulfonamide group, or a hydroxy group. 5. The copolymer according to any of claims 1 to 3, characterized in that A2 is of the formula: where : R is hydrogen, methyl or ethyl, Ri is absent or represents from one to four alkyl substituents, alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups, U2 is absent or represents an amide or ester linker, V2 is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, and wherein R2 each time it occurs is independently hydrogen or alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups. 6. The copolymer according to claim 5, characterized in that Y is. 8. The copolymer according to any of claims 1 to 7, characterized in that c varies between about 0.01 and about 0.90. 9. The copolymer according to any of claims 1 to 8, characterized in that A3 comprises an alkyl or aryl pendant group, and aryl which is optionally substituted with alkyl. 10. The copolymer according to claim 9, characterized in that A3 is of the formula: where R is hydrogen, methyl or ethyl, U3 is absent or is an amide or ester linker, and Z is alkyl or aryl, alkyl that is optionally substituted with one or more of hydroxy, alkyloxy or halide and the aryl which is optionally substituted with one or more alkyls that are optionally substituted with one or more of hydroxy, alkyloxy or halide. 11. The copolymer according to claim 10, characterized in that A3 is: wherein R is hydrogen, methyl or ethyl. 12. The copolymer according to any of claims 1 to 11, characterized in that A4 comprises a pendant group comprising a carboxylic acid group or a phosphoric acid group. 13. The copolymer according to claim 12, characterized in that A4 is of the formula: wherein R is hydrogen, methyl or ethyl, Ri is absent or represents from one to four alkyl substituents; alkyl substituents optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide, or carbamate functional groups, U4 is absent or represents an amide or ester linker, V4 is absent or represents alkyl optionally comprising one or more ether, ester, amine, amide, urea, piperazinyl, sulfonamide or carbamate functional groups, and -COOH, -PO (OH) 2, - 4-COOH 14. The copolymer according to claim 12, characterized in that A4 is a monomeric unit obtained by polymerizing monomers of acrylic acid, methacrylic acid, 4-carboxyphenylmethacrylamide, 4-carboxyphenylacrylamide, vinylbenzoic acid, vinyl phosphoric acid, methacrylyl-alkyl phosphoric, or acrylyl-alkyl-phosphoric acid. 15. A coating composition, sensitive to near-infrared radiation, characterized in that it comprises: a copolymer as defined in any of claims 1 to 14; a binder resin; an almost-infrared radiation absorption compound; Y optional additives. 16. A lithographic, thermal, positive working printing plate, characterized in that it comprises an almost-infrared radiation sensitive coating, the coating being a coating prepared from the coating composition of claim 15. 17. A positive working thermal lithographic printing plate, characterized in that it comprises a coating sensitive to near-infrared radiation, the coating comprising: a copolymer as defined in any of claims 1 to 13; a binder resin; a compound that absorbs near-infrared radiation; Y optional additives. 18. A method for producing a lithographic, thermal, positive working printing plate, the method is characterized in that it comprises the steps of: a) provide a substrate, and b) coating the composition of the coating of claim 15 on the substrate. 19. A printing method, the method is characterized in that it comprises the steps of: a) providing a lithographic, thermal, positive working printing plate according to claim 16 or 17, b) Imaging the printing plate with near-infrared radiation, c) reveal the printing plate, and d) using the printing plate in a printing press for printing. 20. A monomer corresponding to a monomeric unit Al of the formula: 83 It varies between 1 and 10. 21. A monomer, characterized in that it corresponds to a monomeric unit A2 of the formula
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CN106886129B (en) * | 2017-03-28 | 2021-01-26 | 广东潮新科数字科技有限公司 | Positive thermosensitive photosensitive composition and application thereof in developing-free CTP (computer to plate) |
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2010
- 2010-09-14 JP JP2013527426A patent/JP5593447B2/en not_active Expired - Fee Related
- 2010-09-14 KR KR1020137001103A patent/KR101471310B1/en active IP Right Grant
- 2010-09-14 RU RU2012153993/04A patent/RU2559050C2/en not_active IP Right Cessation
- 2010-09-14 WO PCT/CA2010/001401 patent/WO2011006265A2/en active Application Filing
- 2010-09-14 CN CN201080067245.6A patent/CN103038267B/en not_active Expired - Fee Related
- 2010-09-14 BR BR112012030319A patent/BR112012030319A2/en not_active Application Discontinuation
- 2010-09-14 CA CA2809726A patent/CA2809726C/en not_active Expired - Fee Related
- 2010-09-14 US US13/822,976 patent/US9822206B2/en not_active Expired - Fee Related
- 2010-09-14 AU AU2010273146A patent/AU2010273146B2/en not_active Ceased
- 2010-09-14 UA UAA201213887A patent/UA106533C2/en unknown
- 2010-09-14 ES ES10799339T patent/ES2570379T3/en active Active
- 2010-09-14 EP EP10799339.6A patent/EP2566900B1/en not_active Not-in-force
- 2010-09-14 MX MX2012014326A patent/MX336236B/en unknown
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- 2013-03-15 HK HK13103271.9A patent/HK1176368A1/en not_active IP Right Cessation
Also Published As
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JP2013540845A (en) | 2013-11-07 |
AU2010273146B2 (en) | 2014-06-19 |
HK1176368A1 (en) | 2013-07-26 |
CN103038267B (en) | 2015-09-30 |
WO2011006265A4 (en) | 2011-09-22 |
CA2809726A1 (en) | 2011-01-20 |
KR20130043157A (en) | 2013-04-29 |
AU2010273146A1 (en) | 2012-12-13 |
JP5593447B2 (en) | 2014-09-24 |
AU2010273146A2 (en) | 2013-01-31 |
WO2011006265A3 (en) | 2011-07-21 |
EP2566900A2 (en) | 2013-03-13 |
US20140221591A1 (en) | 2014-08-07 |
US9822206B2 (en) | 2017-11-21 |
RU2012153993A (en) | 2014-06-20 |
BR112012030319A2 (en) | 2016-08-09 |
RU2559050C2 (en) | 2015-08-10 |
UA106533C2 (en) | 2014-09-10 |
MX336236B (en) | 2016-01-11 |
CA2809726C (en) | 2015-12-15 |
EP2566900A4 (en) | 2014-02-19 |
CN103038267A (en) | 2013-04-10 |
ES2570379T3 (en) | 2016-05-18 |
WO2011006265A2 (en) | 2011-01-20 |
EP2566900B1 (en) | 2016-02-17 |
KR101471310B1 (en) | 2014-12-09 |
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